Manufacture of alkyl aryl hydrocarbons



Patented Dec. 12, 1950 MANUFACTURE or 1mm ARYL maocaaaous Edward J. Schwoegler, Hammond, Ind., aaaignol' to Wyandotte Chemicals Corporation, Wyandotte, Mich., a corporation of Michigan No Drawing. Application September 25, 1947,

Serial No. 776.153

The present invention relates to an improvement in the process of making alkyl aryl sulfonic acids and the salts thereof, as derived from petroleum hydrocarbon distillates and aromatic hydrocarbons of the benzene series, such as benzene, toluene, xylene, etc. The process of this invention .relates particularly to the production of the intermediate alkyl aryl hydrocarbon compounds which are subsequently sulfonated to produce the alkyl aryl sulfonic acids, the latter being then neutralized with an alkali, such as caustic soda, to produce the well known-type of wetting agent, surface active agent and detergent, namely: sodium alkyl aryl sulfonates.

In the production of such alkyl aryl hydrocarbons, it is customary to chlorinate a petroleum hydrocarbon distillate whose bofling point range occurs within the kerosene range; and then. to condense the resultant alkyl chloride with benzene, toluene, xylene or the like, by means of a Friedel-Crafts condensation reagent such as anhydrous aluminum chloride. Such alkyl aryl hydrocarbon compounds, due to the fact that the alkyl group thereof is derived from a petroleum hydrocarbon distillate in the kerosene range, have laterally become termed by those skilled in the art as kerylbenzenesf' In the synthesis of such keryl benzenes, the selection of the petroleum hydrocarbon distillate or'cut" as it is more popularly known in the petroleum refining art, has been the subject of considerable effort and investigation by prior in-.

ventors. These prior efforts in the selection of the petroleum distillate "cut" have fallen into two general categories: (1) the selection of a narrow boiling range (1. e., where the initial and final boiling points are separated by a relatively small temperature difference) petroleum hydrocarbon distillate fraction and (2) the selection of a wide boiling range petroleum distillate fraction. Thus, for example. Kyrides U. 8. Patent No. 2,161,174 prefers petroleum distillate frac' tions having a narrow boiling range, such as one boiling ov the range of 244-260 C. (a 18 terminal point difi'erence); Thomas U. 8. Patent No. 2,210,962 selects a range of 300-330 C. (a terminal boiling point difference) and Kyrides U. 8. Patent No. 2,218,472 selects a boiling range of 205-245" C. (a 40 terminal boiling point difference). on the other hand, Guenther U. 8. Patent No. 2,220,099 discloses the use of a relatively wide boiling range petroleum hydrocarbon distillate fraction, viz: 150-300 C. (a 150 terminal boiling point difference); Flett U. 8. Patent No. 2,267,725 discloses another wide 6 Claims. ((31. 260-671) boiling range, viz: 185-275' C. (a terminal boiling point difference) and Flett U. 8. Patent No. 2,283,199 discloses still another wide boiling range of petroleum hydrocarbon distillate, viz:

210-290 C. (an 80 terminal boiling point difference).

Thus it is seen that prior workers in the art have disclosed that it is desirable to go to either one of two comparative extremes in the selection of the petroleum hydrocarbon distillate fraction, for the purported objective of obtaining either better yields, improved detergent properties, or both. One group of these prior contributors to the art have preferred to operate in the relatively close terminal boiling point differences of 16-40 C.; and the other group has preferred tooperate in the relatively wide terminal boil- .ing point differences of 80-150 C.' The initial and final boiling points of all of these previously employed petroleum hydrocarbon distillate fractions will be found to fall within limits corresponding to the boiling points of-alkyl hydrocarbons ranging from nonane to heptadecan'e', i. e. those having 9-17 carbon atoms. (See Cross: Handbook .of Petroleum, Asphalt and Natural Gas" 1931 edition, p. 202; and The Science of Petroleum," Oxford University Press, 1938 edition, vol. II, pp. 13264347.)

I have made the discovery that when two dif ferent petroleum hydrocarbon distillate fractions. one fraction having a boiling range occurring at relatively low temperatures and the other having a boiling range occurring at relatively hi h temperatures, the two ranges being disparate and not overlapping or continuous with respect to each other, that most unexpected and gr a ly improved yields of alkyl benzenes, are obtained; particularly when a mixture of the two disparate boiling range fractions is chlorinated to an extent corresponding to above and up wan-% degree of monochlorination. The alkyl aryl sulfonate products produced from the resultant alkyl aryl hydrocarbons or k'eryl benzenes possess excellent wetting, surface active and detergent properties.

When the yields of the alkyl aryl hydrocarbons from the individual petroleum distillate fractions are compared with the yield obtained from the mixture of such disparate boiling range fractions, it is found that the result is of a synergistic character, inasmuch as the yields in the case of such mixtures are greater than could have been mathematically calculated or interpolated from the yields of the individual petroleum hydrocarbon distillate fractions.

Preferabb' the best results are obtained when the relatively low and relatively high boiling point range distillate fractions are admixed in the amount of -30% by volume of the relatively low boiling point range distillate fraction component and 70-90% by volume of the relatively high boiling point range distillate fraction component.

More precisely, I prefer to employ a petroleimi hydrocarbon distillate boiling in the range of 165-205 C., and this boiling range corresponding to alkyl hydrocarbons consisting predominantly of decane and undecane, and the saturated isomers thereof; and a petroleum hydrocarbon distillate fraction boiling in the range of 212-245 C., the latter fraction consisting predominantly of tridecane and its saturated isomers. These preferred petroleum hydrocarbon distillate fractions moreover, are preferably admixed in the amount of 10-80% by volume of the 165-205 C. boiling range fraction and 70-90% by volume of the 212-245 C. boiling range fraction. The resultant mixture of distillate fractions is chlorinated to an extent corresponding to between 50% and 100%.degree of monochlorination (based upon the average molecular weight of the hydrocarbons in the mixture) The resultant chlorinated mixture of hydrocarbons is then condensed with benzene,-toluene, xylene or the like, in the presence of more than 2% and less than 5% by weight of anhydrous aluminum chloride on the basis of the alkyl chloride or keryl chloride; to produce the desired intermediate alkyl aryl hydrocarbon. The latter product may of course then be sulfonated and neutralized to produce albl aryl sulfonate.

It has been found that 50% monochlorination of the hydrocarbon fractions mixture is a wellpronounced lower limit of the specified range. The above mentioned increase in yields in alhl aryl hydrocarbons becomes practically imperceptible at 50% monochlorination. whereas at 55% monochlorination, the yield increase is at least 25% over and above that of the individual hydrocarbon fractions alone. Thus, if a curve were to be plotted showing increase in yield versus degree as of chlorination, such curve would show a sharp break or rise at the degree of monochlorination ordinate.

The following examples will serve to illustrate my invention in greater detail.

Example 1 A mixture of 10% by volume of petroleum bon distillate fraction boiling in the range of 165-205 C. and by volume of a fraction boiling in the range of 212-245 C., was chlorinated in the presence of light, to an extent corresponding to monochlorination (based on a molecular weight of 184 for the hydrocarbon fractions mixture). It is of interest to here note that the boiling range of the resultant mixture of distillate fractions was not the same as that of the total range covered by the lowest and highest end-boiling points of the individual fractions before mixing, but was found to be 192-245 C. The alkyl chlorides thus produced were then condensed with an equal weight of benzene in the presence of 4.9% by weight of anhydrous aluminum chloride based upon the weight of the alkyl chloride mixture. After the completion of the reaction, and after separation of the spent catalyst sludge, the reaction mass was distilled to remove unreacted benzene. The yield of alkyl benleum hydrocarbon distillate fraction mixture employed as a starting product, was 72%.

Example 1(a) By way of comparison of yields of the above described mixture of relatively low and relatively higher boiling point range petroleum hydrocarbon distillate fractions with the yield of albl benzene from each one of the fractions alone, the following procedures were employed:

The petroleum hydrocarbon distillate fraction boiling in the range of -205 C. was chlorinated to the extent of 100% degree of monochlorination (based on a molecular weight of 149 of the hydrocarbon), the resultant alkyl chloride condensed with an equal weight of benzene in the same manner as in Example 1, and the unreacted benzene and petroleum hydrocarbon distillate distilled oil. The resultant yield of alkyl benzene was 83% based upon the weight of petroleum hydrocarbon distillate fraction starting product. The petroleum hydrocarbon distillate fraction boiling in the range of 212-245 C. was similarly chlorinated to 100% monochlorination, condensed with an equal weight of benzene, and the unreacted benacne and petroleum hydrocarbon distillate removed by distillation. 'I'he yield of alkyl benzene. based upon the weight of petroleum hydrocarbon distillate fraction starting product was 50%.

Example 2 A mixture was prepared consisting of 30% by volume petroleum hydrocarbon distillate fraction boiling in the range of 165-205 C. and 70% by volume of petroleum hydrocarbon distillate fraction boiling in the range of 212-245" C. The bollins range of the resultant mixture of distillate fractions was -245 C. This mixture of distillate fractions was chlorinated to 100% monochlorination, the resultant alkyl chloride subsequently condensed then with an equal weight of benzene, in the same manner as in Example 1. The resultant yield of alkyl benzene was 62% of the weight of the mixture of petroleum hydrocarbon distillate fractions employed as the starting product.

distillate fractions as used in Example 1, was emplayed in the instant example and then 1500 grams of this mixture and'0.04% of iodine were .placed in a 3 liter round bottom flask equipped with a thermometer, condenser. scrubber system and dispersing tube. Chlorine was introduced into the kerosene through the, disperser. At first the chlorine did not react but dissolved in the kerosene. At the end of approximately a ten minute induction period the chlorine reacted as it was being introduced. The temperature of chlorination was held between 3840 C. by external cooling. Chlorination continued until the kerosene increased in weight by 222 grams. This required 2 hours. The chlorine content is equivalent to 12.9% of the chlorinated alkyl halide mixture, representing 79% monochlorination based on the calculation that the hydrocarbons present had an average molecular weight of 184.

One thousand seven hundred twenty-two grams of benzene boiling over a 1 C. range were placedina 5-liter 3-neck round bottom flask equipped with an agitator, condenser, thermometer and an addition funnel. Anhydrous aluminum chloride in the amount of 4.9% by weight sene, based upon the amount by weight of petroon the basis of the alkyl halides present, was

assault ture rose from 27 to 30' C. and' the hydrochloric acid gas formed in the reaction was removed through the scrubber system. When the reaction was nearly completed as evidenced by a substantial decrease in the evolution of hydrochloricacidgas, the mixture was heated at 70 C. for l benzene as a condensation catalyst.

hour. The mass was allowed to settle for 8 hours.

The catalyst complex was drawn oi! anddiscarded. The upper oil layer was placed in a '5-liter round bottom flask equipped with a thermometer and agitator and 29.3 grams of an acid clay were added. This quantity of clay is equivalent to approximately 1% by weight of the oil. The mixture was agitated for 96 hour at room temperature. The clay was removed by filtration and the crude alkylation mixture was fractionated at atmospheric pressure to remove unreacted benzene'and kerosene; 794 grams of the alkyl-aryl hydrocarbon remained in the distillation pot as a residue. This corresponded to a yield of 53% based upon the original 1500 grams of petroleum hydrocarbon distillate fractions The resultant alkyl arylhydrocarbon mixture was subsequently sulfonated with sulfuric acid. the lower spent acid layer removed. The upper sulionic acid layer was dissolved in water and neutralized with 50% caustic soda solution. A sodium alkyl aryl sulfonate-sodium sulfate prodnot was thereby produced, such product being in the amount of 1034 grams of which 810'grams or 78% by weight was sodium alkyl aryl sulfonate active ingredient. Anhydrous sodlum,Na2SO4 in the amount of 946 grams was added to the solution and the latter was dried on a double drum dryer, producing 1980 grams of solid dry sodium alkyl aryl sulfonate-NazSOr mixture, containing 41% by weight of sodium alkyl aryl sulfonate activeingredient. i

Example 3(a) For the purpose of comparison of the yields of the mixture of petroleum hydrocarbon distillate fractions of Example 3 with those of the individual distillate fractions alone, both the 165- 205- C. boiling range fraction and the 212-245 C. boiling range fraction were individually chlorinated to 80% degree of monochlorination. Upon subsequent condensation with benzene and rethe standard of the American Petroleum Institute, designated as A. P. I. No. 507-540. See A. 8. T. M. Standards on Petroleum Products and Lubricants," prepared by A. B. T. M. Committee D-2, October 1944 edition.

Other members of the benzene series or benzene'family," such as toluene and xylene, or mixtures of benzene, toluene and/or xylene, can beemployedinplaceoithebenzenealonoofthe foregoing examples, and with equivalent results. Other modes of applying the principle of my invention may be employed, changes being made as regards to the details described, provided the features stated in any 01' the following claims or the equivalent of such be employed. I, therefore, particularly point out and distinctly claim as my inventioni 1. The method of making alkyl aryl hydrocarbons as an intermediate in the manufacture of alkyl aryl sulfonates, comprising admixing a relatively low boiling petroleum distillate fraction in the kerosene range, consisting predominantly of 10-11 carbon atom alkyl hydrocarbons, and a relatively higher boiling petroleum distillate fraction in thekerosene range consisting predominantly of 13 carbon atom alkyl hydrocarbons, chlorinating the resultant mixture to an extent corresponding to above 50% and up to monochlorination, and condensing the chlorinated' hydrocarbon mixture with a member of the benzene series in the presence of aluminum chloride.

2. The method of making alkyl aryl hydrocarbons as an intermediate in the manufacture of alkyl aryl sulfonates, comprising admixing a relatively low boiling petroleum distillate fraction in the kerosene range, consisting predominantly of 10-11 carbon atom alkyl hydrocarbons, and a relatively higher boiling petroleum distillate fraction in the kerosene range consisting predominantly of 13 carbon atom alkyl hydrocarbons, the boiling ranges of each of said fractions-being disparate and non-overlapping with respect to each other, chlorinating the resultant mixture to an extent corresponding to above 50% and up to 100% monochlorination, and condensing the chlorinated hydrocarbon mixture with a member of the benzene series in the presence of aluminum chloride.

3. The method of making alkyl aryl hydrocarbons as an intermediate in the manufacture of alkyl aryl sulfonates, comprising admixing 10-'30% by volume of a relatively low boiling petroleum distillate fraction in the kerosene range, consisting predominantly of 10-11 carbon atom alkyl hydrocarbons, with 70-90% by volume of a relatively higher boiling petroleum distillate fraction in the kerosene range consisting predominantly of 13 carbon atom alkyl hydrocarbons, chlorinating the resultant mixture to an extent corresponding to above 50% and up to 100% monochlorination, and condensing the chlorinated hydrocarbon mixture with a member of the benzene series in the presence of aluminum chloride.

. 4. The method of making alkyl aryl hydrocarbons as an intermediate in the manufacture of alkyl aryl sulfonates, comprising admixing 10-30% by volume of a relatively low boiling petroleum distillate fraction in the kerosene range, consisting predominantly of 10-11 carbon atom alkyl hydrocarbons, with 70-90% by volume of a relatively higher boiling petroleum distillate fraction in the kerosene range, consisting predominantly of 13 carbon atom alkyl hydrocarbons, the boiling ranges of each of said fractions being disparate and non-overlapping with respect to each other, chlorinating the resultant mixture to an extent corresponding to above 50% .and up to 100% monochlorination and condensing the chlorinated hydrocarbon mixture with a member of the benzene series in the presence of aluminum chloride.

5. The method of making alkyl aryl hydrocarbone as an intermediate in the manufacture of alhl aryl sulfonates, comprising admixing a relatively low boiling petroleum distillate fraction boiling in the range of 165-206 C. and a relatively higher boiling petroleum distillate fraction boiling in the range of 212-245 C., 'chlorinating the resultant mixture to an extent corresponding to above 50% and up to 100% monochlorination, and condensing the chlorinated hydrocarbon mixture with a member of the benzene series in the presence of aluminum chloride.

6. The method of making alkyl aryl hydrocarbons as an intermediate in the manufacture of alkyl aryl sulfonates, comprising admixing 10- 30% by volume of a relatively low boiling petroleum distillate fraction boiling in the range of 165-205 (3., with 70-90% by volume of a relatively higher boiling petroleum distillate fraction 8 boiling in the range of 212-245 0., chlorinating the resultant mixture to an extent corresponding to above 50% and up to 100% monochlorination, and condensing the chlorinated hydrocarbon 5 mixturewithamemberofthebenaeneseriesin the presence of aluminum chloride.

EDWARD J. SCHWOEGLER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Bill Mar. 9, 1948 

1. THE METHOD OF MAKING ALKL ARYL HYDROCARBONS AS AN INTERMEDIATE IN TEH MANUFACTURE OF ALKYL ARYL SULFONATES, COMPRISING ADMIXING A RELATIVELY LOW BOILING PETROLEUM DISTILLATE FRACTION IN THE KEROSENE RANGE, CONSISTING PREDOMINANTLY OF 10-11 CARBON ATOM ALKYL HYDROCARBONS, AND A RELATIVELY HIGHER BOILING PETROLEUM DISTILLATE FRACTION IN TEH KEROSENE RANGE CONSISTING PREDOMINANTLY OF 13 CARBON ATOM ALKY HYDROCARBONS, CHLORINATING THE RESULTANT MIXTURE TO AN EXTENT CORRESPONDING TO ABOVE 50% AND UP TO 100% MONOCHLORINATION, AND CONDENSING THE CHLORINATED HYDROCARBON MIXTURE WITH A MEMBER OF THE BENZENE SERIES IN TEH PRESENCE OF ALUMINUM CHLORIDE. 